Glycol monoborates



United States Patent 3,131,203 GLYCOL MQNGEGRATES William G. Woods, Anaheim, Calif., assignor to United States Borax Chemical Corporation, Los Angeles, (Salli, a corporation of Nevada No Drawing. Filed May 7, E62, Ser. No. 193,013 Claims. (Cl. 260-462) The present invention relates to a new class of glycol monoborate compounds, the quaternary ammonium alkyl glycol monoborate halides, and has further reference to a method for preparing the same.

it is, therefore, the principal object of the present invention to provide as new compositions the quaternary ammonium alkyl glycol monoborate halides.

It is a further object of this invention to provide a method for preparing the quaternary ammonium alityl glycol monoborate halides.

Other objects of the present invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various Ways in which the principle of the invention may be employed.

Broadly stated, the present invention comprises the quaternary ammonium aikyl glycol monoborate halides of the formula where R is an alhylene radical of from 2 to 3 carbon atoms in length and containing a total of from 2 to 20 carbon atoms, R is an allrylene radical of from 2 to 3 carbon atoms in length and containing a total of from 2 to 5 carbon atoms, R and R are alkyl radicals of from 1 to 18 carbon atoms, R, is selected from the group consisting of benzyl, allyl, and primary alkyl of from 1 to 18 carbon atoms, and X is selected from the group consisting of bromine, chlorine and iodine.

The quaternary ammonium a'll'yl glycol monoborate halides of the present invention have a wide variety of industrial applic tions. They can be used in resins and coating compositions as anti-static agents. They have use as active bactericides and fungicides in soap, detergents and in dry cleaning compositions, and they are effective herbicides when used alone or in combination with other phytotoxie ma erials. Additionally, the present compounds have utility as bacteriostatic agents which prevent microbiological degradation and sludge formation when added to hydrocarbon fuels such as gasoline, jet engine fuels and diesel fuels.

The method for prepa ing the quaternary ammonium alkyl glycol monoborate halides can best be illustrated by the following equation:

where R, R R R R and X are as defined in the foregoing broadly stated paragraph. The reaction will 3,131,208 Patented Apr. 28,1964

proceed when there is an excess of either reactant present. Such excess, however, tends to interfere with the separation of the desired product from the reaction mass, and for the sake of economy and ease of separation, in

the preferred embodiment of the invention, I use equi- 10131 amounts of the reactants.

The preferred method for performing the above reaction is a direct single-step process which involves admixing an aminoalkyl glycol monoborate ester with an applicable organohalide, with or without the presence of a heat transfer medium which is inert to the reactants. The reaction mixture is heated to a temperature of from about 50 C. to about 250 C. and the desired quaternary ammonium alkyl glycol monoborate halide is recovered from the resultant reaction mass. I

It will be noted that when the organohalide reactant used in the present invention is a lower alkyl halide of from 1 to 3 carbon atoms, the reactant is a gas at the stated reaction temperatures. Therefore, when employing alkyl halides of from 1 to 3 carbon atoms as reactants, I perform the present process in a closed system, to more adequately utilize the reactant by preventing its escape from the reaction system.

it will also be noted -that the present reaction will proceed with or Without employing an inert solvent as a heat transfer medium. However, the reaction proweds more readily and the recovery of a substantially pure product is easier when a solvent or heat transfer medium is present, and in the preferred embodiment of the invention the reaction is carried out in the presence of a solvent which is inert to the reactants. The common hydrocarbon solvents such as benzene, n-heptane, xylene, aliphatic naphtha, toluene, etc, are inert to the present reactants and are typical of the solvents which are applicable in the present process.

Referring to the reactants applicable to the present invention, the first of these are the aminoalkyl glycol monoborate esters having the foimula where R is an alkylene radical of from 2. to 3 carbon atoms in length and containing a total of from 2 to 20 carbon atoms, R is an alkylene radical of from 2 to 3 carbon atoms in length and containing a total of from 2 to 5 carbon atoms, and R and R are alkyl radicals of from 1 to 18 carbon atoms. The aminoalkyl glycol monoborate esters are obtained by reacting boric acid or boron tiioxide with an applicable glycol and an applicable aminoalkanol. The following example is given to lllustrate a method for producing these compounds.

A mixture of 103.2 grams (1.00 mole) of N,Ndimethyl- 1-am-1'no-2-propanol, 61.84 grams (1.00 mole) of boric acid, and 90.12 grams (1.00 mole) of 2,3-butanediol was placed in a 2-liter round-bottomed flask containing 400 of benzene. The flask was equipped \with a reflux condenser, a Dean-Stark trap and a magnetic stirrer, and was heated under reflux for about 8 to 10 hours at which time the theoretical amount of Water, 54 ml., had been removed. The excess benzene was then removed by distillation and 149.4 grams (74.3% yield) of Z-(B-dimethylaminoisopropoxy) 4,5 dimethyl 1,3,2 dioxaborolane was recovered, B.P. 131-132 C. (33-85 mm), 11 (24.5 C.) =1.452. Chemical analysis of the product yielded the following data:

Calculated for C H BNO The following list is illustrative of the aminoalkyl glycol monoborate esters applicable to the present invention:

2-(fl-diisopropylaminoethoxy) 1,3,2 dioxaborolane Z-(fi-dioctadecylaminoethoxy) 4 methyl-1,3,2-dioxaborinane 2-(fi-dimethylaminoisopropoxy) 4,5 dimethyl-1,3,2-dioxaborolane 2-(fi-di n hexylaminoisopropoxy)-4,4,6-trimethyl-1,3,2-

dioxaborinane 2-('y-diethylaminopropoxy) 4,5 dimethyl-1,3,2-dioxohorolane 2-( -diisoamylpropoxy) 1,3,2 dioxaborinane 2-(N,N-dimethyl ,8 methyl v aminopropxy)-5- methyl-S-ethyl-I,3,2-dioxaborinane 2- (N, N-di-n-octyl fl methyl-' -aminopropoxy)-4-rnethyl- 1,3,2-dioxaborolane 2(N,N-di-n-propyl [3,5 dimethyl- -aminopropoxy)-4,

4,6-trimethyl-1,3,2-dioxaborinane 2-(N;N-diisohutyl 18,19 dimethyl-y-aminopropoxy)1,3,2-

dioxaborolane Z-(N-rnethyl-N-n-butyl 8 aminoethoxy)-4-propyl-5- ethyl-1,3,2-diox-aborinane 2-(N-ethyl-N-octadecyl- B aminoisopropoxy 4,4,6 trimethyl-1,3,2-dioxaborinane 2-(N-isopropyl N octyl-y-aminopropoxy)-4-methyl- 1,3,2-dioxaborolane 2-(N-methyl N ethyl-5,5-dimethyl-y-aminopropoxy)- 4-methyl-1,3,2-dioxaborolane The second group of reactants are the organohalides having the formula XR where R is either a primary alkyl radical of from 1 to 18 carbon atoms, benzyl or allyl, and X is either bromine, chlorine, or iodine. The following list is illustrative of such compounds:

Methyl iodide Methyl bromide Ethyl chloride n-Propyl chloride n-Butyl bromide n-Amyl chloride n-Hexyl iodide n-Heptyl chloride n-Octyl chloride n-Decyl iodide n-Dodecyl bromide n-Hexadecyl iodide n-Octodecyl bromide n-Hexyl chloride Benzyl chloride Benzyl bromide Allyl chloride Allyl iodide It is to be clearly understood that the foregoing lists are only a partial enumeration of the reactants applicable to the present invention and are in no Way intended to limit the invention.

So that the present invention can be more clearly understood, the following examples are given for illustrative purposes:

Calculated for C H BClNO Percent B 3.17 Cl 10.38

4 Found in product:

Percent B 3.11 C1 9.84

Calculated fOI' C1 H33BC1NO3:

Percent Cl 10.63 Found in product:

A mixture of 51.44 grams (0.20 mole) of Z-(q -diethylaminopropoxy) 5 methyl 5 ethyl-1,3,2-dioxaborinane and 28.39 grams (0.20 mole) of methyl iodide were placed in an autoclave under .a nitrogen atmosphere. The autoclave was heated at from about C. to about 200 C. for about 4 hours. The reaction mass was allowed to cool to about ambient temperature, and the volatile materials were removed from the autoclave by distillation at reduced pressure to yield the desired product, 2-(7-diethylmethylammoniumpropoxy) 5 methyl 5 ethyl-1, 3,2-di0xaborinane iodide. Chemical analysis of the produot yielded the following data:

Calculated for C H BINO Percent I 31.80 Found in product:

Percent Br 17.75 Found in product:

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

where R is an alkylene radical of from 2 to 3 carbon atoms in length and containing a total of from 2 to 20 carbon atoms, R is an alkylene radical of from 2 to 3 carbon atoms in length and containing a total of from 2 to 5 carbon atoms, R and R are alkyl of from 1 to 18 carbon atoms, R; is selected from the group consisting of benzyl, allyl, and primary alkyl of from 1 to 18 carbon atoms, and X is a halogen selected from the group consisting of bromine, chlorine and iodine.

2. 2 (/8 dimethylbenzylarnmoniumethoxy) -4,4,6-trimethyl-1,3,2-dioxaborinane chloride.

3. 2 (t3 diisopropylallylarnmoniumisopropoxy)-4,5- dimethyl-l,3,2-dioxaborolane chloride.

4. 2 ('y diethylmethylammoniumpropoxy)-5methy1- S-ethyl-l,3,2-dioxaborinane iodide.

5. 2 (B diethyl'dodecylammoniumethoxy)-4-rnethyl- 10 1,3,2-dioxaborolane bromide.

References Cited in the file of this patent UNITED STATES PATENTS 2,883,373 Bossard et a1. Apr. 21, 1959 2,972,508 Kruckenberg et a1 Feb. 21, 1961 

1. QUATERNARY AMMONIUM ALKYL GLYCOL MONOBORATE HALIDES OF THE FORMULA 